U.S. patent number 9,518,154 [Application Number 14/304,152] was granted by the patent office on 2016-12-13 for fluorine-containing surface treatment agent and an article treated with the same.
This patent grant is currently assigned to SHIN-ETSU CHEMICAL CO., LTD.. The grantee listed for this patent is SHIN-ETSU CHEMICAL CO., LTD.. Invention is credited to Noriyuki Koike, Yuji Yamane.
United States Patent |
9,518,154 |
Yamane , et al. |
December 13, 2016 |
Fluorine-containing surface treatment agent and an article treated
with the same
Abstract
The invention provides a surface treatment agent wherein a
fluorooxyalkylene group-containing polymer or a fluorooxyalkylene
group-containing polymer composition comprising the polymers, which
is controlled of a temperature range of vaporization of
fluorooxyalkylene group-containing polymer(s). The
fluorooxyalkylene group-containing polymer has a fluorooxyalkylene
structure represented by --(OCF2)p(OCF2CF2)q-- and hydrolysable
groups bond to a silicon atom represented by the formula at least
one terminal. The polymer composition shows a decrease of 75% or
more in weight, relative to the total weight of the polymer, in a
temperature range of from 150 to 350 degrees C. when this is heated
at a rate of 2 degrees C. per minute and a pressure of 0.1 Pa or
less. The present surface treatment agent forms a coating having
water- and oil-repellency and scratch resistance regardless of a
vapor deposition conditions, in particularly by a vapor deposition
at a mild temperature such as 350 degrees C.
Inventors: |
Yamane; Yuji (Annaka-shi,
JP), Koike; Noriyuki (Annaka-shi, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
SHIN-ETSU CHEMICAL CO., LTD. |
Tokyo |
N/A |
JP |
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Assignee: |
SHIN-ETSU CHEMICAL CO., LTD.
(Tokyo, JP)
|
Family
ID: |
52115873 |
Appl.
No.: |
14/304,152 |
Filed: |
June 13, 2014 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20150004419 A1 |
Jan 1, 2015 |
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Foreign Application Priority Data
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Jul 1, 2013 [JP] |
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2013-138249 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09D
183/14 (20130101); C08G 77/24 (20130101); C09D
183/08 (20130101); Y10T 428/31612 (20150401); C08G
77/46 (20130101); C08K 5/03 (20130101); Y10T
428/31663 (20150401); C08G 77/52 (20130101) |
Current International
Class: |
C08G
77/24 (20060101); C09D 183/08 (20060101); C08G
77/52 (20060101); C09D 7/00 (20060101); C09D
183/14 (20060101); C08G 77/46 (20060101); C08K
5/03 (20060101) |
Field of
Search: |
;428/421,429,447
;524/795,858,860 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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A-2011-116947 |
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Jun 2011 |
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JP |
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A-2012-72272 |
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Apr 2012 |
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JP |
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A-2012-233157 |
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Nov 2012 |
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JP |
|
Primary Examiner: Choi; Ling
Assistant Examiner: Wang; Chun-Cheng
Attorney, Agent or Firm: Oliff PLC
Claims
The invention claimed is:
1. A surface treatment agent comprising a fluorooxyalkylene
group-containing polymer and/or a product obtained by partial
hydrolysis and condensation of the polymer, wherein the
fluorooxyalkylene group-containing polymer has a fluorooxyalkylene
structure represented by
--(OCF.sub.2).sub.p(OCF.sub.2CF.sub.2).sub.q--; wherein p and q
are, independently of each other, an integer of from 5 to 80 and a
total of p and q is 10 to 100, and these parenthesized units may be
sequenced at random; and at least one group represented by the
following formula (1) at at least one terminal; ##STR00012##
wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl
group, X is a hydrolysable group, a is 2 or 3, and c is an integer
of from 1 to 10; and shows a decrease of 75% or more in weight,
relative to the total weight of the polymer, in a temperature range
of from 150 to 350 degrees C. when heated at a rate of 2 degrees C.
per minute and a pressure of 0.1 Pa or less.
2. The surface treatment agent according to claim 1, the
fluorooxyalkylene group-containing polymer is represented by the
following formula (2): ##STR00013## wherein Rf is
--(CF.sub.2).sub.d--(OCF.sub.2).sub.p(OCF.sub.2CF.sub.2).sub.q(OCF.sub.2C-
F.sub.2CF.sub.2).sub.r(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.s--O(CF.sub.-
2).sub.d-, A is a fluorine atom, a hydrogen atom, or a monovalent
fluorinated group having a --CF.sub.3 group or a --CF.sub.2H group
at a terminal, Q is a divalent organic group, Z is a divalent to
octavalent organopolysiloxane residue having siloxane bonds, R, X,
a and c are as defined for the aforesaid formula (1), b is an
integer of from 1 to 7, .alpha. is 0 or 1, d is an integer of from
0 to 5, p and q are, independently of each other, an integer of
from 5 to 80, r and s are, independently of each other, an integer
of from 0 to 80, and a total of p, q, r and s is 10 to 100, and
these parenthesized units may be sequenced at random.
3. A surface treatment agent comprising a fluorooxyalkylene
group-containing polymer composition, wherein the composition
comprises a fluorooxyalkylene group-containing polymer having a
fluorooxyalkylene structure represented by
--(OCF.sub.2).sub.p(OCF.sub.2CF.sub.2).sub.q-; wherein p and q are,
independently of each other, an integer of from 5 to 80 and a total
of p and q is 10 to 100, and these parenthesized units may be
sequenced at random; and at least one group represented by the
following formula (1) at at least one terminal; ##STR00014##
wherein R is an alkyl group having 1 to 4 carbon atoms or a phenyl
group, X is a hydrolysable group, a is 2 or 3, and c is an integer
of from 1 to 10; and/or a product obtained by partial hydrolysis
and condensation of said polymer; and an another polymer
represented by the following formula (3): A-Rf-A (3) wherein Rf is
--(CF.sub.2).sub.d--(OCF.sub.2).sub.p(OCF.sub.2CF.sub.2).sub.q(OCF.sub.2C-
F.sub.2CF.sub.2).sub.r(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.s--O(CF.sub.-
2).sub.d-, d is an integer of from 0 to 5, p and q are,
independently of each other, an integer of from 5 to 80, r and s
are, independently of each other, an integer of from 0 to 80, and a
total of p, q, r and s is 10 to 100, A is a fluorine atom, a
hydrogen atom, or a monovalent fluorinated group having a
--CF.sub.3 group or a --CF.sub.2H group at a terminal, and these
parenthesized units may be sequenced at random, and shows a
decrease of 75% or more in weight, relative to the total weight of
the polymer composition, in a temperature range of from 150 to 350
degrees C. when heated at a rate of 2 degrees C. per minute and a
pressure of 0.1 Pa or less.
4. The surface treatment agent according to claim 3, wherein the
fluorooxyalkylene group-containing polymer is represented by the
following formula (2): ##STR00015## wherein Rf is
--(CF.sub.2).sub.d--(OCF.sub.2).sub.p(OCF.sub.2CF.sub.2).sub.q(OCF.sub.2C-
F.sub.2CF.sub.2).sub.r(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.s--O(CF.sub.-
2).sub.d-, A is a fluorine atom, a hydrogen atom, or a monovalent
fluorinated group having a --CF.sub.3 group or a --CF.sub.2H group
at a terminal, Q is a divalent organic group, Z is a divalent to
octavalent organopolysiloxane residue having siloxane bonds, R, X,
a and c are as defined for the aforesaid formula (1), b is an
integer of from 1 to 7, .alpha. is 0 or 1, d is an integer of from
0 to 5, p and q are, independently of each other, an integer of
from 5 to 80, r and s are, independently of each other, an integer
of from 0 to 80, and a total of p, q, r and s is 10 to 100, and
these parenthesized units may be sequenced at random; or
represented by the following formula (4): ##STR00016## wherein Rf
is
--(CF.sub.2).sub.d--(OCF.sub.2).sub.p(OCF.sub.2CF.sub.2).sub.q(OCF.sub.2C-
F.sub.2CF.sub.2).sub.r(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.s--O(CF.sub.-
2).sub.d-, and Q, Z, R, X, a, b, c, d, .alpha., p, q, r and s are
as defined for said formula (2), or is a mixture of the polymers
represented by the formulas (2) and (4).
5. The surface treatment agent according to claim 2 or , wherein Q
is a hydrocarbon group having 2 to 12 carbon atoms and may have one
or more bonds selected from the group consisting of an amide bond,
an ether bond, an ester bond, a silphenylene bond, a silethylene
bond and an alkylene bond.
6. The surface treatment agent according to claim 1, further
comprising a fluorinated solvent.
7. An article treated by vapor deposition with the surface
treatment agent according to claims 1.
8. The article according to claim 7 wherein the article is one
selected from a glass, a hard coat film, a highly hard film, an
anti-reflection film, an ophthalmic lens, an optical lens and a
quartz substrate.
9. The article according to claim 8 wherein the glass is a tempered
glass.
10. The article according to claim 8 wherein the glass is an
anti-reflection coating glass.
11. A method for preparing the surface treatment agent according to
claim 3 wherein the method comprises a step of subjecting a
fluorooxyalkylene group-containing polymer composition comprising a
fluorooxyalkylene group-containing polymer having at least one
group represented by said formula (1) and/or a product obtained by
partial hydrolysis and condensation of said polymer and a polymer
represented by said formula (3) to molecular distillation at a
temperature in a range from 100 to 400 degrees C. to thereby remove
low boiling components and/or high boiling components.
12. The surface treatment agent according to claim 1, wherein the
fluorooxyalkylene group-containing polymer has one group
represented by said formula (1) at at least one terminal.
13. The surface treatment agent according to claim 2, wherein the
fluorooxyalkylene group-containing polymer has one group
represented by said formula (1) at at least one terminal.
14. The surface treatment agent according to claim 3, wherein the
fluorooxyalkylene group-containing polymer has one group
represented by the said formula (1) at at least one terminal.
15. The surface treatment agent according to claim 4, wherein the
fluorooxyalkylene group-containing polymer has one group
represented by said formula (1) at at least one terminal.
16. The surface treatment agent according to claim 1, wherein the
fluorooxyalkylene group-containing polymer has more than one group
represented by said formula (1) at at least one terminal.
17. The surface treatment agent according to claim 2, wherein the
fluorooxyalkylene group-containing polymer has more than one group
represented by said formula (1) at at least one terminal.
18. The surface treatment agent according to claim 3, wherein the
fluorooxyalkylene group-containing polymer has more than one group
represented by said formula (1) at at least one terminal.
19. The surface treatment agent according to claim 4, wherein the
fluorooxyalkylene group-containing polymer has more than one group
represented by formula (1) at at least one terminal.
Description
This application claims the benefits of Japanese Patent application
No. 2013-138249 filed on Jul. 1, 2013, the contents of which are
hereby incorporated by reference.
FIELD OF THE INVENTION
The present invention relates to a fluorine-containing surface
treatment agent and an article treated with the agent.
BACKGROUND OF THE INVENTION
Compounds containing a perfluorooxyalkylene moiety generally have a
very small surface free energy and, accordingly, have good water-
and oil-repellency, chemical resistance, lubricity, a releasing
property, and an antifouling property. Taking advantage of these
properties, they are widely used as, for example, water- and
oil-repellent agents or antifouling agents for paper and fiber,
lubricants for magnetic storage media, oil-repellent components for
precision apparatuses, releasing agents, cosmetics, and protective
coatings. Recently, there is an increasing need for technology to
attain fingerprint proofness or easy removal of fouling on a
surface of a display for better appearance or visibility.
Perfluorooxyalkylene compounds are used as a material to meet these
requirements. In particular, perfluoropolyethers comprising
(CF.sub.2O) units are preferable because of their good lubricity.
For instance, FOMBLIN Z type
[(CF.sub.2O).sub.p(CF.sub.2CF.sub.2O).sub.q] is commercialized.
However, FOMBLIN Z type has wide molecular weight distribution, so
that a polymer synthesized from the FOMBLIN Z type
perfluoropolyether has a wide temperature range of vaporization.
Therefore, there is a problem such that properties of a coating
vary depending on vacuum deposition conditions. Further, it is
difficult to control a degree of vacuum and a temperature rise rate
of a surface treatment agent, so that properties of a coating vary
among batches even when the same apparatus is used.
Japanese Patent Application Laid-Open Nos. 2011-116947, 2012-233157
and 2012-72272, hereinafter called Patent Literatures 1 to 3,
discloses surface treatment agents comprising a composition which
comprises a mixture of a fluorooxyalkylene group-containing polymer
whose main chain is --(OC.sub.2F.sub.4).sub.e(OCF.sub.2).sub.fO--
and which has a hydrolysable group at one terminal, and a
fluorooxyalkylene group-containing polymer having hydrolysable
groups at the both terminals, wherein an amount of the
fluorooxyalkylene group-containing polymer having hydrolysable
groups at the both terminals is specified. Patent Literatures 1 to
3 also describe that the surface treatment agents can form a water-
and oil-repellent layer having excellent scratch resistance and a
lower dynamic friction coefficient. Patent Literature 1: Japanese
Patent Application Laid-Open No. 2011-116947 Patent Literature 2:
Japanese Patent Application Laid-Open No. 2012-233157 Patent
Literature 3: Japanese Patent Application Laid-Open No.
2012-72272
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
However, when the surface treatment agents described in Patent
Literatures 1 to 3 are applied on a surface of a substrate by vapor
deposition, a coating sometimes has poor water- and oil-repellency
and scratch resistance, depending on deposition conditions.
Further, the surface treatment agents in Patent Literatures 1 to 3
are vapor deposited in vacuum at a so high temperature as 740
degrees C. Then, the temperature rises quickly, so that the surface
treatment agent occurs a flash boiling and a coating obtained tends
to be uneven. Therefore, it is preferred to carry out the vapor
deposition gradually at a mild temperature such as 350 degrees C so
as to form an even coating. However, when the surface treatment
agents described in Patent Literatures 1 to 3 are subjected to
vapor deposition at a mild temperature such as 350 degrees C, a
scrub resistance against steel wool of a coating obtained is
poor.
The purpose of the present invention is to provide a surface
treatment agent which stably forms a coating having good water- and
oil-repellency and scratch resistance, regardless of vapor
deposition conditions, in particular by a vapor deposition at a
mild temperature.
Means to Solve the Problems
The present inventors have made research and found that control of
a temperature range of vaporization of fluorooxyalkylene
group-containing polymer(s) comprised in a surface treatment agent
stably attains a formation of a coating having good water- and
oil-repellency and scratch resistance, regardless of vapor
deposition conditions, in particular by vapor deposition in mild
temperature conditions such as 350 degrees C.
Thus, the present invention provides a surface treatment agent
comprising a fluorooxyalkylene group-containing polymer and/or a
product obtained by partial hydrolysis and condensation of the
polymer, wherein the fluorooxyalkylene group-containing polymer has
a fluorooxyalkylene structure represented by
--(OCF.sub.2).sub.p(OCF.sub.2CF.sub.2).sub.q--; wherein p and q
are, independently of each other, an integer of from 5 to 80 and a
total of p and q is 10 to 100, and these parenthesized units may be
sequenced at random; and at least one group represented by the
following formula (1) at at least one terminal;
##STR00001## wherein R is an alkyl group having 1 to 4 carbon atoms
or a phenyl group, X is a hydrolysable group, a is 2 or 3, and c is
an integer of from 1 to 10; and shows a decrease of 75% or more in
weight, relative to the total weight of the polymer, in a
temperature range of from 150 to 350 degrees C when heated at a
rate of 2 degrees C per minute and a pressure of 0.1 Pa or
less.
Further, the present invention provides a surface treatment agent
comprising a fluorooxyalkylene group-containing polymer
composition, wherein the composition comprises a fluorooxyalkylene
group-containing polymer having a fluorooxyalkylene structure
represented by --(OCF.sub.2).sub.p(OCF.sub.2CF.sub.2).sub.q--;
wherein p and q are, independently of each other, an integer of
from 5 to 80 and a total of p and q is 10 to 100, and these
parenthesized units may be sequenced at random; and at least one
group represented by the following formula (1) at least one
terminal;
##STR00002## wherein R is an alkyl group having 1 to 4 carbon atoms
or a phenyl group, X is a hydrolysable group, a is 2 or 3, and c is
an integer of from 1 to 10; and/or a product obtained by partial
hydrolysis and condensation of said polymer; and an another polymer
represented by the following formula (3): A-Rf-A (3) wherein Rf is
--(CF.sub.2).sub.d--(OCF.sub.2).sub.p(OCF.sub.2CF.sub.2).sub.q(OCF.sub.2C-
F.sub.2CF.sub.2).sub.r(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.s--O(CF.sub.-
2).sub.d--, d is an integer of from 0 to 5, p and q are,
independently of each other, an integer of from 5 to 80, r and s
are, independently of each other, an integer of from 0 to 80, and a
total of p, q, r and s is 10 to 100, A is a fluorine atom, a
hydrogen atom, or a monovalent fluorinated group having a
--CF.sub.3 group or a --CF.sub.2H group at a terminal, and these
parenthesized units may be sequenced at random, and shows a
decrease of 75% or more in weight, relative to the total weight of
the polymer composition, in a temperature range of from 150 to 350
degrees C when heated at a rate of 2 degrees C per minute and a
pressure of 0.1 Pa or less.
Further, the present invention provides a method for preparing the
surface treatment agent, wherein the method comprises a step of
subjecting a fluorooxyalkylene group-containing polymer composition
comprising a fluorooxyalkylene group-containing polymer having at
least one group represented by said formula (1) and/or a product
obtained by partial hydrolysis and condensation of said polymer,
and a polymer represented by said formula (3) to molecular
distillation at a temperature in a range from 100 to 400 degrees C
to thereby remove low boiling components and/or high boiling
components.
Effects of the Invention
The surface treatment agent of the present invention stably forms a
coating having good water- and oil-repellency and scratch
resistance regardless of vapor deposition conditions, in particular
by vapor deposition at a mild temperature such as 350 degrees
C.
BEST MODES OF THE INVENTION
The present invention will be described below in detail.
One of the characteristics of the present invention is that the
fluorooxyalkylene group-containing polymer or the fluorooxyalkylene
group-containing polymer composition has molecular weight
distribution such that when the polymer is heated at a rate of 2
degrees C per minute and a pressure of 0.1 Pa or less, the polymer
shows a decrease of 75% or more in weight, relative to the total
weight of the polymer or the composition, which means 75% or more
of the polymer vaporizes, in a temperature range of from 150 to 350
degrees C. Preferably, the decrease in weight is 80% or more,
particularly 90% or more, relative to the total weight of the
polymer or the composition, in the temperature range of from 150 to
350 degrees C.
On account of the fact that the polymer or the composition
comprised in the surface treatment agent has the aforesaid decrease
in weight, the coating stably has a high quality water- and
oil-repellent layer, regardless of vapor deposition conditions. If
a large amount of lower molecular weight components having a
vaporization temperature of lower than 150 degrees C are contained
in a surface treatment agent, a coating obtained has a poor scrub
resistance against steel wool. If a large amount of higher
molecular weight components having a vaporization temperature of
higher than 350 degrees C are contained in a surface treatment
agent, it is difficult to conduct vapor deposition of a surface
treatment agent at a mild temperature, such as 350 degrees C, and a
longer time is required and, therefore, the terminal groups of the
polymer may decompose.
To determine the decrease in weight, the polymer or the composition
is heated at a rate of 2 degrees C per minute and a pressure of 0.1
Pa or less. The polymer may be subjected to a thermogravimetry in
vacuum such as 1.0.times.10.sup.-3 to 9.0.times.10.sup.-2 Pa and
temperatures of from 25 up to 500 degrees C. Any known apparatus
may be used and not limited to any particular one. For instance, a
saturation vapor pressure evaluation system VPE-9000SP, ex
ULVAC-RIKO, Inc. can be used.
The first aspect of the present invention provides a surface
treatment agent comprising a fluorooxyalkylene group-containing
polymer and/or a product obtained by partial hydrolysis and
condensation of the polymer. The fluorooxyalkylene group-containing
polymer has a fluorooxyalkylene structure represented by
--(OCF.sub.2).sub.p (OCF.sub.2CF.sub.2).sub.q-- wherein p and q
are, independently of each other, an integer of from 5 to 80 and a
total of p and q is 10 to 100, and these parenthesized units may be
sequenced at random; and has at least one group represented by the
following formula (1) at at least one terminal;
##STR00003## wherein R is an alkyl group having 1 to 4 carbon atoms
or a phenyl group, X is a hydrolysable group, a is 2 or 3, and c is
an integer of from 1 to 10.
The first aspect of the present invention is characterized in that
when the fluorooxyalkylene group-containing polymer is heated at a
rate of 2 degrees C per minute and a pressure of 0.1 Pa or less,
the polymer shows a decrease of 75% or more, preferably 80% or
more, further preferably 90% or more, in weight, relative to the
total weight of the polymer, in a temperature range of from 150 to
350 degrees C. On account of this characteristic, the present
surface treatment agent forms a coating having good water- and
oil-repellency and scratch resistance. The polymer having molecular
weight distribution to give the aforesaid decrease in weight is
prepared by rectification or molecular distillation of a polymer.
In particular, the molecular distillation is preferred in view of
heating process. The manner of the molecular distillation will be
explained below.
The fluorooxyalkylene group-containing polymer is particularly
represented by the following formula (a): A.sup.0-Rf.sup.0--B.sup.0
(a) wherein Rf.sup.0 is a divalent linear fluorooxyalkylene group
having 5 to 200, preferable 10 to 100, further preferably 10 to 80,
more preferably 20 to 60, --OC.sub.kF.sub.2k-- repeating units,
wherein k is an integer of from 1 to 6, provided that the number of
(OCF.sub.2) units is 5 to 80, the number of (OCF.sub.2CF.sub.2)
units is 5 to 80, and the total number of (OCF.sub.2) and
(OCF.sub.2CF.sub.2) units is 10 to 100. A.sup.0 and B.sup.0 are,
independently of each other, the following Rf.sup.1 or the group
represented by the formula (1).
In the formula (a), Rf.sup.1 is a fluorine atom, a hydrogen atom,
or a monovalent fluorinated group having a --CF.sub.3 group or a
--CF.sub.2H group at a terminal, provided that at least one of
A.sup.0 and B.sup.0 is the group represented by the formula (1).
Rf.sup.0 is particularly a fluorooxyalkylene group represented by
--(CF.sub.2).sub.d--(OCF.sub.2).sub.p(OCF.sub.2CF.sub.2).sub.q(OCF.sub.2C-
F.sub.2CF.sub.2).sub.r(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.s--O(CF).sub-
.d--, wherein d is an integer of from 0 to 5, p and q are,
independently of each other, an integer of from 5 to 80, r and s
are, independently of each other, an integer of from 0 to 80 and a
total of p, q, r and s is 10 to 100, and these parenthesized units
may be sequenced at random.
The fluorooxyalkylene group-containing polymer may have the group
represented by the aforesaid formula (1) at one terminal (that is,
one of A.sup.0 and B.sup.0 is the group represented by the formula
(1) and the other is a Rf.sup.1 group, hereinafter called
"one-terminal hydrolysable polymer"), or at the both terminals
(that is, both of A.sup.0 and B.sup.0 are the group represented by
the formula (1), hereinafter called "both-terminal hydrolysable
polymer"). The polymer may be a mixture of the one-terminal
hydrolysable polymer and the both-terminal hydrolysable polymer.
When the polymer is the mixture, the mixing ratio is not limited to
any particular one, as long as the mixture has molecular weight
distribution such that when the mixture is heated at a rate of 2
degrees C per minute and a pressure of 0.1 Pa or less, the mixture
shows a decrease of 75% or more, preferably 80% or more, further
preferably 90% or more, in weight, relative to the total weight of
the mixture, in a temperature range of from 150 to 350 degrees C.
The one-terminal hydrolysable polymer is particularly
preferred.
The one-terminal hydrolysable polymer is represented by the
following formula (2):
##STR00004## wherein Rf is
--(CF.sub.2).sub.d--(OCF.sub.2).sub.p(OCF.sub.2CF.sub.2).sub.q(OCF.sub.2C-
F.sub.2CF.sub.2).sub.r(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.s--O(CF.sub.-
2).sub.d--, A is a fluorine atom, a hydrogen atom, or a monovalent
fluorinated group having a --CF.sub.3 group or a --CF.sub.2H group
at a terminal, Q is a divalent organic group, Z is a divalent to
octavalent organopolysiloxane residue having siloxane bonds, R is
an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a
hydrolysable group, a is 2 or 3, b is an integer of from 1 to 7, c
is an integer of from 1 to 10, a is 0 or 1, d is an integer of from
0 to 5, p and q are, independently of each other, an integer of
from 5 to 80, r and s are, independently of each other, an integer
of from 0 to 80, and a total of p, q, r and s is 10 to 100, and
these parenthesized units may be sequenced at random.
The both-terminal hydrolysable polymer is represented by the
following formula (4):
##STR00005## wherein Rf is
--(CF.sub.2).sub.d--(OCF.sub.2).sub.p(OCF.sub.2CF.sub.2).sub.q(OCF.sub.2C-
F.sub.2CF.sub.2).sub.r(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.s--O(CF.sub.-
2).sub.d--, and Q, Z, R, X, a, b, c, d, a, p, q, r and s are as
defined for the formula (2).
In the afore-mentioned formulas, p and q are, independently of each
other, preferably an integer of from 10 to 60, further preferably
20 to 50, r and s are, independently of each other, preferably an
integer of from 0 to 20, further preferably 0 to 10, and a total of
p, q, r and s is preferably 10 to 80, further preferably 20 to 60,
provided that the p, q, r and s are a number such that the polymer
has molecular weight such that when the polymer is heated at a rate
of 2 degrees C per minute and a pressure of 0.1 Pa or less, the
polymer shows a decrease of 75% or more, preferably 80% or more,
further preferably 90% or more, in weight, relative to the total
weight of the polymer, in a temperature range of from 150 to 350
degrees C.
In the afore-mentioned formula, A is a fluorine atom, a hydrogen
atom, or a monovalent fluorinated group having a --CF.sub.3 group
or --CF.sub.2H group at a terminal, preferably a fluoroalkyl group
having 1 to 6 carbon atoms. The terminal is preferably a
--OCF.sub.3 group or --OCF.sub.2H group.
In the afore-mentioned formulas, X is, independently of each other,
a hydrolysable group. Examples of X include alkoxy groups having 1
to 10 carbon atoms such as methoxy, ethoxy, propoxy and buthoxy
groups; oxyalkoxy groups having 2 to 10 carbon atoms such as
methoxymethoxy and methoxyethoxy groups; acyloxy groups having 1 to
10 carbon atoms such as an acetoxy group; alkenyloxy groups having
2 to 10 carbon atoms such as an isopropenoxy group; and halogen
atoms such as chlorine, bromine, and iodine atoms. Among these,
methoxy, ethoxy, isopropenoxy groups and a chlorine atom are
preferred.
In the afore-mentioned formulas, R is an alkyl group having 1 to 4
carbon atoms and a phenyl group. Among these, a methyl group is
preferred. "a" is 2 or 3, preferably 3 in view of reactivity and
adhesiveness to a substrate. "b" is an integer of from 1 to 7,
preferably 1 to 3, and "c" is an integer of from 1 to 5, preferably
1 to 3.
In the afore-mentioned formulas, Q is a divalent organic group to
link Rf with Z, or Rf with the (CH.sub.2).sub.c group. Preferred
are organic groups with have 2 to 12 carbon atoms and may have one
or more bonds selected from an amide bond, an ether bond, an ester
bond and a vinyl bond, more preferably substituted or unsubstituted
hydrocarbon groups with have 2 to 12 carbon atoms and may have
aforesaid bond. Examples of Q include the following;
##STR00006##
In the afore-mentioned formulas, Z is a divalent to octavalent
organopolysiloxane residue having siloxane bonds. Z is preferably a
linear or cyclic organopolysiloxane residue having 2 to 13 silicon
atoms, preferably 2 to 5 silicon atoms. Z may contain a silalkylene
structure where two silicon atoms are bonded via an alkylene group
and which is represented by Si--(CH.sub.2).sub.n--Si wherein n is
an integer of from 2 to 6. The present fluorooxyalkylene
group-containing polymer has siloxane bonds in the molecule, so
that the present surface treatment agent forms a coating which has
excellent scrub resistance and scratch resistance.
Preferably, the organopolysiloxane residue has an alkyl group
having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, or
a phenyl group. The alkylene group in the silalkylene bond
preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon
atoms.
Examples of Z include the following;
##STR00007##
The present surface treatment agent may comprise a product obtained
by partial hydrolysis and condensation of the aforesaid
fluorooxyalkylene group-containing polymer. The product is obtained
by subjecting the terminal hydrolyzable group(s) of the
fluorooxyalkylene group-containing polymer to partial hydrolysis
and condensation in a conventional manner.
The second aspect of the present invention provides a surface
treatment agent comprising the fluorooxyalkylene group-containing
polymer composition. The composition comprises
a fluorooxyalkylene group-containing polymer having a
fluorooxyalkylene structure represented by --(OCF.sub.2).sub.p
(OCF.sub.2CF.sub.2).sub.q--;
wherein p and q are, independently of each other, an integer of
from 5 to 80 and a total of p and q is 10 to 100, and these
parenthesized units may be sequenced at random; and at least one
group represented by the following formula (1) at at least one
terminal;
##STR00008## wherein R is an alkyl group having 1 to 4 carbon atoms
or a phenyl group, X is a hydrolysable group, a is 2 or 3, and c is
an integer of from 1 to 10; and/or _ps a product obtained by
partial hydrolysis and condensation of said polymer; and an another
polymer represented by the following formula (3), hereinafter
called "non-terminal hydrolysable polymer": A-Rf-A (3) wherein Rf
is
--(CF.sub.2).sub.d--(OCF.sub.2).sub.p(OCF.sub.2CF.sub.2).sub.q(OCF.sub.2C-
F.sub.2CF.sub.2).sub.r(OCF.sub.2CF.sub.2CF.sub.2CF.sub.2).sub.s--O(CF.sub.-
2).sub.d--, d is an integer of from 0 to 5, p and q are,
independently of each other, an integer of from 5 to 80, r and s
are, independently of each other, an integer of from 0 to 80, and a
total of p, q, r and s is 10 to 100, A is a fluorine atom, a
hydrogen atom, or a monovalent fluorinated group having a
--CF.sub.3 group or a --CF.sub.2H group at a terminal.
The fluorooxyalkylene group-containing polymer is particularly
represented by the aforesaid formula (a). It is preferred that the
fluorooxyalkylene group-containing polymer is the one-terminal
hydrolysable polymer represented by the aforesaid formula (2), the
both-terminal hydrolysable polymer represented by the aforesaid
formula (4), or a mixture of the one-terminal hydrolysable polymer
and the both-terminal hydrolysable polymer. The mixing ratio of the
one-terminal hydrolysable and/or both-terminal hydrolysable
polymers and the non-terminal hydrolysable polymer is not limited
to any particular one, as long as the composition has molecular
weight distribution such that when the polymer composition is
heated at a rate of 2 degrees C per minute and a pressure of 0.1 Pa
or less, the polymer composition shows a decrease of 75% or more,
preferably 80% or more, further preferably 90% or more, in weight,
relative to the total weight of the polymer composition, in a
temperature range of from 150 to 350 degrees C. In particular, the
present composition preferably comprises the one-terminal
hydrolysable polymer represented by the aforesaid formula (2) as a
main component.
The second aspect of the present invention is characterized in that
when the fluorooxyalkylene group-containing polymer composition is
heated at a rate of 2 degrees C per minute and a pressure of 0.1 Pa
or less, the polymer composition shows a decrease of 75% or more,
preferably 80% or more, further preferably 90% or more, in weight,
relative to the total weight of the polymer composition, in a
temperature range of from 150 to 350 degrees C. On account of this
characteristic, the present surface treatment agent attains a
formation of a coating anytime having good water- and
oil-repellency and scratch resistance. A composition having the
aforesaid decrease in weight is prepared by rectification or
molecular distillation of a mixture of the one-terminal
hydrolysable and/or the both-terminal hydrolysable polymers and the
non-terminal hydrolysable polymer, and/or a partial hydrolysis and
condensation of these polymers. In particular, the molecular
distillation is preferred in view of heating process.
In the first and second aspects of the present invention, any
molecular distillation apparatus can be used and not limited to any
particular one. Examples of the molecular distillation apparatus
include pot molecular distillation apparatus, falling film
molecular distillation apparatus, centrifugal molecular
distillation apparatus, thin-film distillation apparatus and
thin-film evaporators. The molecular distillation may be conducted
in a vacuum of a pressure of 0.1 Pa or less and a temperature of
100 to 400 degrees C. In particular, it is preferred that the
molecular distillation is carried out in a high vacuum at a
temperature of from 100 to 300 degrees C to thereby remove low
boiling components and, then, at a higher temperature of from 150
to 400 degrees C to thereby remove high boiling components. When
the composition has narrow boiling point distribution, either one
of the aforesaid steps may be enough. A higher degree of vacuum
allows one to obtain a desired product at a relative lower
temperature. For instance, the pressure is 1.0.times.10.sup.-3 to
50.times.10.sup.-3 Pa.
The surface treatment agent may further comprise a catalyst for
hydrolysis and condensation reactions, if needed. Examples of the
catalyst include organic tin compounds such as dibutyltin
dimethoxide and dibutyltin dilaurate; organic titanium compounds
such as tetra-n-butyl titanate; organic acids such as acetic acid,
methanesulfonic acid and fluorinated carboxylic acid; and inorganic
acids such as hydrochloric acid and sulfuric acid. Among these,
preferred are acetic acid, tetra-n-butyl titanate, dibutyltin
dilaurate and fluorinated carboxylic acid. A content of the
catalyst may be a catalytic amount, which ranges typically from
0.01 to 5 parts by mass, particularly from 0.1 to 1 part by mass,
per 100 parts by mass of the fluorooxyalkylene group-containing
polymer and/or the product obtained by partial hydrolyzation and
condensation of the polymer.
The surface treatment agent may comprise a solvent. Examples of the
solvent include fluorinated aliphatic hydrocarbon solvents such as
perfluoroheptane and perfluoroctane; fluorinated aromatic
hydrocarbon solvents such as m-xylenehexafluoride, bezotrifluoride
and 1,3-trifluoromethylbenzene; fluorinated ether solvents such as
methyl perfluorobutyl ether, ethyl perfluorobutyl ether, and
perfluoro(2-butyltetrahydrofuran); fluorinated alkylamine solvents
such as perfluorotributylamine and perfluorotripentylamine;
hydrocarbon solvents such as petroleum benzene, mineral spirits,
toluene and xylene; ketone solvents such as acetone,
methylethylketone and methylisobutylketone. Among these,
fluorinated solvents are preferred in view of solubility and
wettability of the surface treatment agent. Particularly preferred
are 1,3-trifluoromethylbenzene, m-xylenehexafluoride,
perfluoro(2-butyltetrahydrofuran), perfluorotributylamine and ethyl
perfluorobutyl ether.
A mixture of two or more of the aforesaid solvents may be used.
Preferably, the fluorooxyalkylene group-containing polymer and/or
the product obtained by partial hydrolyzation and condensation of
the polymer are dissolved homogeneously. An optimum concentration
of the fluorooxyalkylene group-containing polymer in a solvent may
be decided, depending on treatment conditions, and is usually from
0.01 to 30 wt %, preferably from 0.02 to 20 wt %, further
preferably from 0.05 to 5 wt %.
The present surface treatment agent may be applied on a substrate
by vapor deposition to form a good coating. Examples of a method
for the vapor deposition include a resistance heating method and an
electronic beam heating method, but are not limited thereto. The
present surface treatment agent may be applied on a substrate by
brushing, dipping, spraying or spinning. The surface treatment
agent may be cured in conditions selected depending on the applying
method. When the surface treatment agent is applied by brushing or
dipping, a curing temperature is preferably from ambient
temperature, i.e. 20 plus or minus 15 degrees C, to 200 degrees C.
The curing is carried out preferably in a humid environment to
promote the curing reaction. A thickness of a cured coating may be
selected depending on the type of a substrate, and is typically
from 0.1 nm to 100 nm, particularly from 1 to 20 nm.
A substrate to be treated with the present surface treatment agent
may be various substrates, such as paper, cloths, metals and metal
oxides, glasses, plastics, ceramics and quartz, but is not limited
to these. The present surface treatment agent provides water- and
oil-repellency, a low dynamic friction coefficient and scratch
resistance to these substrates. In particular, the present surface
treatment agent is used suitably for glasses treated with SiO.sub.2
and for quartz substrates.
Examples of an article to be treated with the present surface
treatment agent include glasses, hard coat films, highly hard
films, anti-reflection films, ophthalmic lenses, optical lenses and
quartz substrates. In particular, the present surface treatment
agent is suitable to form a water- and oil-repellent layer on a
surface of tempered glasses and anti-reflection coating
glasses.
EXAMPLES
The present invention will be explained in detail by reference to
the Examples and the Comparative Examples, but shall not be limited
thereto.
A mixture used in the following Synthesis Example 1 comprised 95
mole % of a polymer represented by the following formula (1a) and 5
mole % of a polymer represented by the following formula (1b). The
mixture was prepared by partially fluorinating a perfluorooxy
compound having carboxylic groups at the both terminals with a
fluorine gas. The polymers having carboxylic group(s) were adsorbed
on an anion exchange resin and separated and, thereby, the mixing
ratio was controlled. The mixing ratio of the polymer in mole % was
determined by .sup.19F-NMR analysis.
F.sub.3C(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.2COOH
(1a) F.sub.3C(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.3
(1b) (p/q=1.0, a total number of p and q was nearly equal 46)
Synthesis Example 1
50 Grams of the mixture of 95 mole % of the polymer represented by
the formula (1a) and 5 mole % of the polymer represented by the
formula (1b) was dissolved in a mixed solvent of 40 g of
1,3-trifluoromethylbenzene and 10 g of tetrahydrofuran. 30 Grams of
a 40% solution of sodium bis(2-methoxyethoxy)aluminum hydride in
toluene was added dropwise to the mixture and stirred at room
temperature for 3 hours, to which an appropriate amount of
hydrochloric acid was subsequently added and stirred well to make
the mixture neutralized and, then, washed with water. A lower phase
was taken out and subjected to distillation to remove the solvents
to obtain 40 g of a liquid product. According to .sup.19F-NMR
analysis, the product obtained comprised 95 mole % of a polymer
represented by the following formula (2a) and 5 mole % of a polymer
represented by the following formula (2b).
F.sub.3C(OC.sub.2F.sub.4)(OCF.sub.2).sub.p--OCF.sub.2CH.sub.2OH
(2a) F.sub.3C(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.3
(2b) (p/q=1.0, a total number of p and q was nearly equal 46)
In a reactor, 40 g of the mixture of 95 mole % of the polymer
represented by the formula (2a) and 5 mole % of the polymer
represented by the formula (2b), 3.5 g of allyl bromide and 0.4 g
of tetrabutylammonium hydrogen sulfate were placed and stirred at
50 degrees C for 3 hours. 5.2 Grams of an aqueous 30% sodium
hydroxide solution was added dropwise and aged at 55 degrees C for
12 hours. Then, appropriate amounts of PF 5060 and hydrochloric
acid were added and stirred, and washed well with water. The lower
phase was taken out and subjected to distillation to remove the
solvents to obtain 30 g of a liquid product. According to
.sup.19F-NMR and .sup.1H-NMR analysis, the product obtained
comprised 95 mole % of a polymer represented by the following
formula (3a) and 5 mole % of a polymer represented by the following
formula (3b), hereinafter called "composition A".
F.sub.3C(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.2CH.sub.2OCH.su-
b.2CH.dbd.CH.sub.2 (3a)
F.sub.3C(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.3 (3b)
(p/q=1.0, a total number of p and q was nearly equal 46)
Synthesis Example 2
Subsequently, 30 g of composition A obtained, 20 g of
1,3-trifluoromethylbenzene, 3 g of trimethoxysilane and 0.1 g of a
solution of a chloroplatinic acid/vinyl siloxane complex in
toluene, containing 2.5.times.10.sup.-8 mole of Pt, were mixed and
aged at 70 degrees C for 3 hours. Then, the solvent and unreacted
compounds were distilled off under a reduced pressure of 533 Pa at
100 degrees C to obtain 25 g of a liquid product. According to
.sup.1H-NMR analysis, the product obtained comprised 95 mole % of a
polymer represented by the following formula (1-a) and 5 mole % of
a polymer represented by the following formula (1-b), hereinafter
called "composition 1-1".
F.sub.3C(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.2CH.sub.2OC.sub-
.3H.sub.6Si(OCH.sub.3).sub.3 (1-a)
F.sub.3C(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.3 (1-b)
(p/q=1.0, a total number of p and q was nearly equal 46)
Composition 1-1 was subjected to molecular distillation at
2.times.10.sup.-2 Pa and 180 degrees C to thereby remove low
boiling components. The composition obtained is hereinafter called
"composition 1-2". A recovery ratio was 70%.
Composition 1-1 was subjected to molecular distillation at
2.times.10.sup.-2 Pa and 320 degrees C to thereby remove high
boiling components. The composition obtained is hereinafter called
"composition 1-3". A recovery ratio was 80%.
Composition 1-1 was subjected to molecular distillation at
2.times.10.sup.-2 Pa and 180 degrees C to thereby remove low
boiling components and, then, subjected to further molecular
distillation at 2.times.10.sup.-2 Pa and 320 degrees C to thereby
remove high boiling components. The composition obtained is
hereinafter called "composition 1-4". A recovery ratio was 52%.
Synthesis Example 3
Grams of composition A, 20 g of 1,3-trifluoromethylbenzene, 10 g of
tetramethylcyclotetrasiloxane and 0.1 g of a solution of a
chloroplatinic acid/vinyl siloxane complex in toluene, containing
2.5.times.10.sup.-8 mole of Pt, were mixed and aged at 70 degrees C
for 3 hours. Then, the solvent and unreacted compounds were
distilled off under a reduced pressure. 30 Grams of the mixture
obtained, 20 g of 1,3-trifluoromethylbenzene, 3.7 g of
allyltrimethoxysilane and 0.1 g of a solution of a chloroplatinic
acid/vinyl siloxane complex in toluene, containing
2.5.times.10.sup.-8 mole of Pt, were mixed and aged at 70 degrees C
for 2 hours. Then, the solvent and unreacted compounds were
distilled off under a reduced pressure of 533 Pa at 100 degrees C
to obtain 29 g of a mixture comprising 95 mole % of a polymer
represented by the following formula (2-a) and 5 mole % of a
polymer represented by the following formula (2-b), hereinafter
called "composition 2-1".
##STR00009## (p/q=1.0, a total number of p and q was nearly equal
46)
Composition 2-1 was subjected to molecular distillation at
2.times.10.sup.-2 Pa and 170 degrees C to thereby remove low
boiling components. The composition obtained is hereinafter called
"composition 2-2". A recovery ratio was 83%.
Composition 2-1 was subjected to molecular distillation at
2.times.10.sup.-2 Pa and 330 degrees C to thereby remove high
boiling components. The composition obtained is hereinafter called
"composition 2-3". A recovery ratio was 71%.
Composition 2-1 was subjected to molecular distillation at
2.times.10.sup.-2 Pa and 170 degrees C to thereby remove low
boiling components and, then, subjected to further molecular
distillation at 2.times.10.sup.-2 Pa and 330 degrees C to thereby
remove high boiling components. The composition obtained is
hereinafter called "composition 2-4". A recovery ratio was 42%. 20
[0050]
Synthesis Example 4
30 Grams of composition A, 20 g of 1,3-trifluoromethylbenzene, 8.1
g of (4-dimethylsilylphenyl)dimethylsilane and 0.1 g of a solution
of a chloroplatinic acid/vinyl siloxane complex in toluene,
containing 2.5.times.10.sup.-8 mole of Pt, were mixed and aged at
70 degrees C for 3 hours. Then, the solvent and unreacted compounds
were distilled off under a reduced pressure. 30 Grams of the
mixture obtained, 20 g of 1,3-trifluoromethylbenzene, 1.5 g of
allyltrimethoxysilane and 0.1 g of a solution of a chloroplatinic
acid/vinyl siloxane complex in toluene, containing
2.5.times.10.sup.-8 mole of Pt, were mixed and aged at 70 degrees C
for 2 hours. Then, the solvent and unreacted compounds were
distilled off under a reduced pressure of 533 Pa at 100 degrees C
to obtain 28 g of a mixture comprising 95 mole % of a polymer
represented by the following formula (3-a) and 5 mole % of a
polymer represented by the following formula (3-b), hereinafter
called "composition 3-1".
##STR00010## (p/q=1.0, a total number of p and q was nearly equal
46)
Composition 3-1 was subjected to molecular distillation at
2.times.10.sup.-2 Pa and 170 degrees C to thereby remove low
boiling components. The composition obtained is hereinafter called
"composition 3-2". A recovery ratio was 85%.
Composition 3-1 was subjected to molecular distillation at
2.times.10.sup.-2 Pa and 330 degrees C to thereby remove high
boiling components. The composition obtained is hereinafter called
"composition 3-3". A recovery ratio was 75%.
Composition 3-1 was subjected to molecular distillation at
2.times.10.sup.-2 Pa and 170 degrees C to thereby remove low
boiling components and, then, subjected to further molecular
distillation at 2.times.10.sup.-2 Pa and 330 degrees C to thereby
remove high boiling components. The composition obtained is
hereinafter called "composition 3-4". A recovery ratio was 53%.
Synthesis Example 5
A mixture used in the following Synthesis Example 5 comprised 52
mole % of a polymer represented by the following formula (4a), 24
mole % of a polymer represented by the following formula (4b) and
24 mole % of a polymer represented by the following formula (4c).
The mixture was prepared by partially fluorinating the perfluorooxy
compound having carboxylic groups at the both terminals with a
fluorine gas. The polymers having a carboxylic group(s) were
adsorbed on an anion exchange resin and separated and, thereby, the
mixing ratio was controlled. The mixing ratio of the polymers in
mole % was determined by .sup.19F-NMR analysis.
F.sub.3C(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.2COOH
(4a) F.sub.3C(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.3
(4b)
HOOC--CF.sub.2--(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.2COOH
(4c) (p/q=1.0, a total number of p and q was nearly equal 46)
50 Grams of the mixture of 52 mole % of a polymer represented by
the formula (4a), 24 mole % of a polymer represented by the formula
(4b) and 24 mole % of a polymer represented by the formula (4c) was
dissolved in a mixed solvent of 40 g of 1,3-trifluoromethylbenzene
and 10 g of tetrahydrofuran. 30 Grams of a 40% solution of sodium
bis(2-methoxyethoxy)aluminum hydride in toluene was added dropwise
to the mixture and stirred at room temperature for 3 hours, to
which an appropriate amount of hydrochloric acid was subsequently
added and stirred well to make the mixture neutralized and, then,
washed with water. A lower phase was taken out and subjected to
distillation to remove the solvents to obtain 40 g of a liquid
product. According to .sup.19F-NMR analysis, the product obtained
comprised 52 mole % of a polymer represented by the following
formula (5a), 24 mole % of a polymer represented by the following
formula (5b) and 24 mole % of a polymer represented by the
following formula (5c).
F.sub.3C(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.2CH.sub.2OH
(5a) F.sub.3C(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.3
(5b)
HOH.sub.2C--CF.sub.2--(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.2-
CH.sub.2OH (5c) (p/q=1.0, a total number of p and q was nearly
equal 46)
In a reactor, 40 g of the mixture of 52 mole % of the polymer
represented by the formula (5a), 24 mole % of the polymer
represented by the formula (5b) and 24 mole % of the polymer
represented by the formula (5c), 3.5 g of allyl bromide and 0.4 g
of tetrabutylammonium hydrogen sulfate were placed and stirred at
50 degrees C for 3 hours. 5.2 Grams of an aqueous 30% sodium
hydroxide solution was added dropwise and aged at 55 degrees C for
12 hours. Then, appropriate amounts of PF 5060 and hydrochloric
acid were added and stirred, and washed well with water. A lower
phase was taken out and subjected to distillation to remove the
solvents to obtain 30 g of a liquid product. According to
.sup.19F-NMR and .sup.1H-NMR analysis, the product obtained
comprised 52 mole % of a polymer represented by the following
formula (6a), 24 mole % of a polymer represented by the following
formula (6b) and 24 mole % of a polymer represented by the
following formula (6c), hereinafter called "composition B",
corresponding to the composition described in Example 1 of Japanese
Patent Application Laid-Open No. 2011-116947, corresponding to US
2011/098402 A1.
F.sub.3C(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.2CH.sub.2OCH.su-
b.2H.dbd.CH.sub.2 (6a)
F.sub.3C(OC.sub.2F.sub.4).sub.q(OCF.sub.2).sub.p--OCF.sub.3 (6b)
CH.sub.2.dbd.CHCH.sub.2OCH.sub.2--CF.sub.2--(OC.sub.2F.sub.4).sub.q(OCF.s-
ub.2).sub.p--OCF.sub.2CH.sub.2OCH.sub.2CH.dbd.CH.sub.2 (6c)
(p/q=0.9, a total number of p and q was nearly equal 45)
Synthesis Example 6
Grams of composition B, 20 g of 1,3-trifluoromethylbenzene, 16.2 g
of 4-(dimethylsilylphenyl)dimethylsilane and 0.1 g of a solution of
a chloroplatinic acid/vinyl siloxane complex in toluene, containing
2.5.times.10.sup.-8 mole of Pt, were mixed and aged at 70 degrees C
for 3 hours. Then, the solvent and unreacted compounds were
distilled off under a reduced pressure of 533 Pa at 100 degrees C.
30 Grams of the mixture obtained, 20 g of
1,3-trifluoromethylbenzene, 3.0 g of allyltrimethoxysilane 16 and
0.1 g of a solution of a chloroplatinic acid/vinyl siloxane complex
in toluene, containing 2.5.times.10.sup.-8 mole of Pt, were mixed
and aged at 70 degrees C for 2 hours. Then, the solvent and
unreacted compounds were distilled off under a reduced pressure to
obtain 27 g of a mixture comprising 52 mole % of a polymer
represented by the following formula (4-a), 24 mole % of a polymer
represented by the following formula (4-b) and 24 mole % of a
polymer represented by the following formula (4-c), hereinafter
called "composition 4-1".
##STR00011## (p/q=0.9, a total number of p and q was nearly equal
45)
Composition 4-1 was subjected to molecular distillation at
2.times.10.sup.-2 Pa and 180 degrees C to thereby remove low
boiling components. The composition obtained is hereinafter called
"composition 4-2". A recovery ratio was 80%.
Composition 4-1 was subjected to molecular distillation at
2.times.10.sup.-2 Pa and 320 degrees C to thereby remove high
boiling components. The composition obtained is hereinafter called
"composition 4-3". A recovery ratio was 70%.
Composition 4-1 was subjected to molecular distillation at
2.times.10.sup.-2 Pa and 180 degrees C to thereby remove low
boiling components and, then, subjected to further molecular
distillation at 2.times.10.sup.-2 Pa and 320 degrees C to thereby
remove high boiling components. The composition obtained is
hereinafter called "composition 4-4". A recovery ratio was 44%.
Decrease in Weight
The each composition was subjected to a thermogravimetry with the
following conditions to measure the weight at temperatures of from
25 up to 500 degrees C. A decrease in weight in a temperature range
of from 150 to 350 degrees C was calculated. The results are as
shown in Table 1.
[Conditions and Apparatus]
Apparatus: Saturation vapor pressure evaluation system VPE-9000SP,
ex ULVAC-RIKO, Inc. Measurement atmosphere: in vacuum,
1.0.times.10.sup.-3 to 9.0.times.10.sup.-2 Pa Heating rate: 2
degrees C per minute Temperature range: 25 to 500 degrees C
TABLE-US-00001 TABLE 1 Decrease in weight, % Composition 1-1 61
Composition 1-2 68 Composition 1-3 60 Composition 1-4 91
Composition 2-1 48 Composition 2-2 56 Composition 2-3 65
Composition 2-4 82 Composition 3-1 52 Composition 3-2 65
Composition 3-3 74 Composition 3-4 84 Composition 4-1 44
Composition 4-2 58 Composition 4-3 55 Composition 4-4 81
Preparation of Surface Treatment Agents
Each of compositions 1-1 to 4-4 was dissolved in
1,3-trifluoromethylbenzene in a 20 wt % concentration to obtain a
surface treatment agent.
Forming of a Coating by Vapor Deposition at 350 Degrees C
The each surface treatment agent was vacuum vapor deposited on a
glass having a size of 50 mm.times.100 mm, Gorilla2, ex Corning
Incorporated, whose upper surface had been vapor deposited with 10
nm of SiO.sub.2 in the following conditions, and was left at 40
degrees C and 80% humidity for 2 hours to form a cured coating.
[Conditions and Apparatus]
Apparatus: Small-sized vacuum vapor deposition equipment VPC-250F,
ex ULVAC-RIKO, Inc. Pressure: 2.0.times.10.sup.-3 Pa to
3.0.times.10.sup.-2 Pa Temperature of vapor deposition, the highest
temperature of a boat: 350 degrees C Distance of vapor deposition:
20 mm Input volume: 10 mg Deposited volume: 10 mg
The cured coatings obtained were evaluated on water- and
oil-repellency, determined dynamic friction coefficient and
evaluated on scrub resistance in the following methods. The results
are as shown in Tables 2 to 5.
Evaluation of Water- and Oil-Repellency
Using a contact angle meter, Drop Master, ex Kyowa Interface
Science Co., Ltd., contact angles of the cured coatings with water
and oleic acid were measured.
Dynamic Friction Coefficient
The dynamic friction coefficient against Bemcot, ex Asahi Kasei,
was determined with a surface property test machine, 14FW, ex
Shinto Scientific Co., Ltd. in the following conditions.
Contact area: 10 mm.times.35 mm
Load: 100 g
Scrub Resistance
Using a rubbing tester, ex Shinto Scientific Co., Ltd., the cured
coating was scrubbed in the following conditions, and then a
contact angle with water was determined. Test environment was 25
degrees C and a humidity of 40%.
1. Scrub Resistance Against a Cloth
Cloth: Bemcot, ex Asahi Kasei Corporation
Scrub distance (one way): 30 mm
Scrub speed: 1800 mm/min
Load: 1 kg/cm.sup.2
Number of scrubbing: 50,000 times
2. Scrub Resistance Against an Eraser
Eraser: EB-SNP, ex TOMBOW Co., Ltd.
Scrub distance (one way): 30 mm
Scrub speed: 1800 mm/min
Load: 1 kg/cm.sup.2
Number of scrubbing: 10,000 times
3. Scrub Resistance Against Steel Wool
Steel wool: BONSTAR #0000, ex Nippon Steel Wool Co., Ltd.
Scrub distance (one way): 30 mm
Scrub speed: 1800 mm/min
Load: 1 kg/cm.sup.2
Number of scrubbing: 5,000 times
TABLE-US-00002 TABLE 2 After scrubbed Initial values Cloth Eraser
Steel wool Decrease Water Oil Dynamic Water Water Water in
repellency repellency friction repellency repellency repellency
Composition weight, % (.degree.) (.degree.) coefficient (.degree.)
(.degree.) (.degree.) Example 1 1-4 91 115 74 0.03 110 110 106
Comparative 1-1 61 114 72 0.04 110 106 92 Example 1 Comparative 1-2
68 113 73 0.03 108 107 85 Example 2 Comparative 1-3 60 112 72 0.03
106 105 91 Example 3
TABLE-US-00003 TABLE 3 After scrubbed Initial values Cloth Eraser
Steel wool Decrease Water Oil Dynamic Water Water Water in
repellency repellency friction repellency repellency repellency
Composition weight, % (.degree.) (.degree.) coefficient (.degree.)
(.degree.) (.degree.) Example 2 2-4 82 114 73 0.03 106 108 110
Comparative 2-1 48 112 71 0.03 106 107 82 Example 4 Comparative 2-2
56 112 73 0.03 103 104 93 Example 5 Comparative 2-3 65 113 72 0.03
105 102 91 Example 6
TABLE-US-00004 TABLE 4 After scrubbed Initial values Cloth Eraser
Steel wool Decrease Water Oil Dynamic Water Water Water in
repellency repellency friction repellency repellency repellency
Composition weight, % (.degree.) (.degree.) coefficient (.degree.)
(.degree.) (.degree.) Example 3 3-4 84 114 73 0.03 110 108 107
Comparative 3-1 52 112 71 0.03 107 103 93 Example 7 Comparative 3-2
65 112 72 0.03 106 103 91 Example 8 Comparative 3-3 74 113 72 0.04
104 107 85 Example 9
TABLE-US-00005 TABLE 5 After scrubbed Initial values Cloth Eraser
Steel wool Decrease Water Oil Dynamic Water Water Water in
repellency repellency friction repellency repellency repellency
Composition weight, % (.degree.) (.degree.) coefficient (.degree.)
(.degree.) (.degree.) Example 4 4-4 81 112 72 0.03 112 105 101
Comparative 4-1 44 111 71 0.04 105 106 65 Example 10 Comparative
4-2 58 112 71 0.04 10 105 75 Example 11 Comparative 4-3 55 111 71
0.04 106 103 81 Example 12
The coatings formed from the surface treatment agents prepared in
Comparative Examples 1, 4, 7 and 10, comprising the compositions
which were not molecular-distilled, i.e., its molecular
distribution was not controlled, which is the same as described in
Patent Literatures 1 to 3, showed poor scrub resistance against
steel wool. The coatings formed from the surface treatment agents
comprising the compositions which showed the smaller decrease in
weight than the lower limit of the present invention had poor scrub
resistance against steel wool. In contrast, all of the coatings
formed from the present surface treatment agents prepared in the
Examples 1 to 4 had good scratch resistance.
Forming of a Coating by Vapor Deposition at 700 Degrees C
The each surface treatment agent was vacuum vapor deposited on a
glass having a size of 50 mm.times.100 mm, Gorilla2, ex Corning
Incorporated, whose outermost surface had been vapor deposited with
10 nm of SiO.sub.2 in the following conditions, and was left at 40
degrees C and 80% humidity for 2 hours to form a cured coating.
[Conditions and Apparatus]
Apparatus: Small-sized vacuum vapor deposition equipment VPC-250F,
ex ULVAC-RIKO, Inc. Pressure: 2.0.times.10.sup.-3 Pa to
3.0.times.10.sup.-2 Pa Temperature of vapor deposition, the highest
temperature of a boat: 700 degrees C Distance of vapor deposition:
20 mm Input volume: 10 mg Deposited volume: 10 mg
The cured coatings obtained were evaluated in the aforesaid
methods. The results are as shown in Tables 6 to 9.
TABLE-US-00006 TABLE 6 After scrubbed Initial values Cloth Eraser
Steel wool Decrease Water Oil Dynamic Water Water Water in
repellency repellency friction repellency repellency repellency
Composition weight, % (.degree.) (.degree.) coefficient (.degree.)
(.degree.) (.degree.) Example 5 1-4 91 114 75 0.03 112 111 110
Comparative 1-1 61 115 73 0.03 109 105 102 Example 13 Comparative
1-2 68 112 73 0.03 107 106 104 Example 14 Comparative 1-3 60 113 73
0.03 105 108 93 Example 15
TABLE-US-00007 TABLE 7 After scrubbed Initial values Cloth Eraser
Steel wool Decrease Water Oil Dynamic Water Water Water in
repellency repellency friction repellency repellency repellency
Composition weight, % (.degree.) (.degree.) coefficient (.degree.)
(.degree.) (.degree.) Example 6 2-4 82 115 75 0.03 108 109 110
Comparative 2-1 48 114 72 0.03 107 108 100 Example 16 Comparative
2-2 56 113 73 0.03 104 104 102 Example 17 Comparative 2-3 65 112 72
0.03 102 103 92 Example 18
TABLE-US-00008 TABLE 8 After scrubbed Initial values Cloth Eraser
Steel wool Decrease Water Oil Dynamic Water Water Water in
repellency repellency friction repellency repellency repellency
Composition weight, % (.degree.) (.degree.) coefficient (.degree.)
(.degree.) (.degree.) Example 7 3-4 84 115 74 0.03 111 108 111
Comparative 3-1 52 113 72 0.03 105 108 105 Example 19 Comparative
3-2 65 113 73 0.03 108 104 108 Example 20 Comparative 3-3 74 113 73
0.03 105 107 94 Example 21
TABLE-US-00009 TABLE 9 After scrubbed Initial values Cloth Eraser
Steel wool Decrease Water Oil Dynamic Water Water Water in
repellency repellency friction repellency repellency repellency
Composition weight, % (.degree.) (.degree.) coefficient (.degree.)
(.degree.) (.degree.) Example 8 4-4 81 113 73 0.03 112 108 110
Comparative 4-1 44 113 78 0.03 103 105 97 Example 22 Comparative
4-2 58 112 73 0.03 107 106 98 Example 23 Comparative 4-3 55 111 71
0.04 105 105 88 Example 24
When the composition is vapor deposited at 700 degrees C, the
temperature rises quickly, so that even components having a
relatively large molecular weight are deposited in an earlier
stage. Accordingly, the scrub resistance against steel wool of the
coating tends to be better, compared to the coating obtained by a
vapor deposition at 350 degrees C. Therefore, even when the surface
treatment agent comprises polymers of Comparative Examples, some of
the coatings formed by a vapor deposition at 700 degrees C had good
scrub resistance against steel wool. However, the scratch
resistances of all of the coatings obtained in the Comparative
Examples was inferior to those of the coatings obtained from the
present surface treatment agents.
When the composition was vapor deposited at 700 degrees C, the
temperature rises quickly, so that a flash boiling may occur and
the coating obtained tended to be uneven. Therefore, it is
preferred to carry out the vapor deposition gradually in mild
conditions such as 350 degrees C so as to obtain an even
coating.
INDUSTRIAL APPLICABILITY
The present surface treatment agent stably forms a coating having
high water- and oil-repellency and scratch resistance regardless of
vapor deposition conditions, in particular by a vapor deposition at
a mild temperature such as 350 degrees C. In particular, the
present surface treatment agent can stably form a high quality
coating, compared to conventional surface treatment agents such as
described in Patent Literatures 1 to 3. Therefore, the present
surface treatment agent is particularly suitable to form a water-
and oil-repellent layer on tempered glass and optical articles such
as touch panel displays and anti-reflection coating films.
* * * * *